CN101120289A - Tubular object and manufacturing method thereof - Google Patents
Tubular object and manufacturing method thereof Download PDFInfo
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- CN101120289A CN101120289A CNA2006800052936A CN200680005293A CN101120289A CN 101120289 A CN101120289 A CN 101120289A CN A2006800052936 A CNA2006800052936 A CN A2006800052936A CN 200680005293 A CN200680005293 A CN 200680005293A CN 101120289 A CN101120289 A CN 101120289A
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- CN
- China
- Prior art keywords
- fluororesin
- tubular articles
- polyimide
- precursor solution
- polyimide precursor
- Prior art date
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- G03G15/2014—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat using heat using contact heat
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- G03G15/2057—Structural details of heat elements, e.g. structure of roller or belt, eddy current, induction heating relating to the chemical composition of the heat element and layers thereof
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- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
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- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G2215/00—Apparatus for electrophotographic processes
- G03G2215/20—Details of the fixing device or porcess
- G03G2215/2003—Structural features of the fixing device
- G03G2215/2009—Pressure belt
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G2215/00—Apparatus for electrophotographic processes
- G03G2215/20—Details of the fixing device or porcess
- G03G2215/2003—Structural features of the fixing device
- G03G2215/2016—Heating belt
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G2215/00—Apparatus for electrophotographic processes
- G03G2215/20—Details of the fixing device or porcess
- G03G2215/2003—Structural features of the fixing device
- G03G2215/2016—Heating belt
- G03G2215/2035—Heating belt the fixing nip having a stationary belt support member opposing a pressure member
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G2215/00—Apparatus for electrophotographic processes
- G03G2215/20—Details of the fixing device or porcess
- G03G2215/2003—Structural features of the fixing device
- G03G2215/2048—Surface layer material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous layer]
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- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
一种管状物体(31)，其是对含有聚酰亚胺和氟树脂粒子的混合物进行成形、加热固化而成的，其特征在于，存在于上述管状物体的表层附近的至少一部分氟树脂粒子，在上述管状物体的外表面或内外表面熔融流动而析出，部分或整面地形成氟树脂被膜。该管状物体(31)可以如下制造：将在聚酰亚胺前体溶液中添加有氟树脂粒子的混合溶液涂敷于模具外表面，流延成形为规定的厚度，进行加热以酰亚胺化，将上述酰亚胺化的最高温度设定为超过氟树脂的熔点的温度，冷却后，将上述模具和管状物体分离而制得。因此，提供一种降低管状物体特别是其外表面的动摩擦系数、耐久性高、制造成本低廉的管状物体及其制造方法。
A tubular object (31) formed by molding and curing a mixture containing polyimide and fluororesin particles, characterized in that at least a part of the fluororesin particles present near the surface of the tubular object, The fluororesin film is formed by melting and flowing on the outer surface or the inner and outer surfaces of the above-mentioned tubular object to form a part or the whole surface. This tubular object (31) can be produced as follows: a mixed solution in which fluororesin particles are added to a polyimide precursor solution is applied to the outer surface of a mold, tape-cast to a predetermined thickness, and heated to imidize , the maximum temperature of the imidization is set to a temperature exceeding the melting point of the fluororesin, and after cooling, the mold is separated from the tubular object. Therefore, there are provided a tubular object with reduced kinetic friction coefficient, especially its outer surface, high durability, and low manufacturing cost and a manufacturing method thereof.
Description
Technical field
The present invention relates to a kind of tubular articles, described tubular articles is in the device for image forming that utilizes electronic photography modes such as duplicating machine, printer, facsimile recorder, by the heat stable resin formation that is used for the toner of not photographic fixing (unfixed) being looked like to carry out hot photographic fixing (fixing), in more detail, relate to a kind of high tubular articles and manufacture method thereof of kinetic friction coefficient, permanance that reduces the surfaces externally and internally of tubular articles.
Background technology
Polyimide resin has excellent characteristic such as thermotolerance, dimensional stability, mechanical property, electrical characteristics, uses in broad field such as electronics, electric equipment and insulating material or aerospace usually.As an example of its purposes, in the image processing system of electronic photography mode, also in electronic photography technologies such as charged, sensitization, intermediate transfer and photographic fixing, use as many members.
At this, the polyimide tubulose object illustrative example that the fixing member as image processing system is used describes.In image processing systems such as duplicating machine, laser printer, the terminal stage in printing and duplicating to looking like to carry out heating and melting with the toner on the sheet transfer materials headed by the paper, makes its photographic fixing on transfer materials.
If enumerate an example that uses the polyimide resin tubular articles as the photographic fixing band of image processing system, the band photographic fixing mode that motion in patent documentation 1～3 grade is arranged, as shown in Figure 6, usually use being formed at the photographic fixing band that toner on the copy paper looks like to carry out hot photographic fixing as being used for.In this purposes, inboard at photographic fixing band 31 (polyimide resin tubular articles) has tape guide 32 and ceramic heater 33, at well heater and have between the backer roll 34 of drive source of crimping and send into the copy paper 37 that is formed with the toner picture on one side successively, make toner 38 heating and meltings on one side, make its photographic fixing on copy paper.Following good feature is arranged: because well heater in fact directly heats toner across the polyimide tubulose object (photographic fixing band) of the tunicle with extremely thin film like in above-mentioned band photographic fixing mode, thereby the instantaneous fixing temperature that reaches regulation in heating part, not from electric power starting to reach can the photographic fixing state stand-by period, in addition, consumption electric power is also little.
In addition, motion has an example in patent documentation 4, forms in the device at full-color image the add pressure zone of polyimide tubulose object as the photographic fixing machine used.This fixing device as shown in Figure 7, it is by the rotatable fixing roller 54 with the drive source that contains thermal source 55, is crimped on adding pressure zone 51 (polyimide resin tubular articles), being disposed at pushing liner 53 and pushing the structure that guide piece 52 constitutes of this inboard that adds pressure zone of this roller, its method is: will add pressure zone and push surface at fixing roller, utilize the driving force of fixing roller to make and add the pressure zone rotation, the copy paper 57 that will be formed with toner image is sent into its clamping connection portion successively, with toner as 56 in the photographic fixing of fixing roller surface heat.The polyimide tubulose object that uses in these purposes generally can be configured as tubular articles by the polyimide precursor solution that will in the polarity polymer solvent tetracarboxylic dianhydride and diamine reactant be obtained, it is carried out imidizate obtains.
The above-mentioned method of making tubular articles by polyimide precursor solution, as described in the patent documentation 5～6, the method of motion is after the outside surface of shaping dies or inside surface are shaped polyimide precursor solution with the thickness of regulation, heating or finish imidizate by chemical method separates and obtains tubular articles from mould.
Above-mentioned photographic fixing band or add the band that pressure zone usually uses 2 layers of structure or 3-tier architecture, described 2 layers of structure are that the outside surface (face that joins with toner) at polyimide tubulose object is formed with somatotype layers such as fluororesin; Described 3-tier architecture is to have the bottom that is used to improve cementability between above-mentioned polyimide tubulose object and fluororesin layer.
In recent years, OA equipment is to the requirement height of miniaturization, high speed, in order to adapt to such requirement, at the photographic fixing band or add in the pressure zone, requires to have the somatotype of the outside surface of band, the low or high characteristics such as heat conductivity of kinetic friction coefficient of inside surface simultaneously.
That is, the pressure zone that adds of the photographic fixing band of above-mentioned Fig. 6 or Fig. 7 forms the mechanism that transmits, rotates by backer roll or the fixing roller with drive source respectively.By this mechanism, when directly contacting with the roller with drive source, the revolving force of driven roller is directly delivered to band, is rotated more sleekly.But,, therefore cause being easy to generate slip on the surface of copy paper and band when between driven roller and band, inserting copy paper, when carrying out toner fixing in fact, the revolving force of being with being delivered to band from driven roller across copy paper.
Particularly the outermost layer of photographic fixing or backer roll is laminated with somatotype layers such as fluororesin for the adhesion (set-off (offset) phenomenon) of the toner that prevents fusion, and kinetic friction coefficient is low to slide easily, and high speed is easy more more slides for duplicating machine and printer.As mentioned above, when when photographic fixing face (clamping part) takes place to slide, by the small slip repeatedly of copy paper and belt surface, thereby the somatotype layer of belt surface is copied paper wearing and tearing fluffing, the chap of somatotype laminar surface, becomes the reason of set-off.
Other problem is, polyimide resin and to be laminated in the original heat conductivity of fluororesin of its outside surface low, and, therefore lack the heat conductivity that adapts to high speed owing to form sandwich construction.
In order to adapt with these requirements, for example motion has patent documentation 7～9 etc.Patent documentation 7 is the inner surface asperitiesization with polyimide tubulose object, keeps lubricant.Patent documentation 8 is to add fluororesin powders such as heat conductivity inanimate matter filling agent and teflon in polyimide precursor, under 250 ℃, heats, then, surface applied fluororesin and form tunicle outside.Patent documentation 9 is also extension of inside surface, the heating that the material that interpolation fluororesin powder in polyimide precursor forms are coated on cylinder mould, makes it be cured reaction.
But the patent documentation 7～9 of above-mentioned existing motion all is to be purpose with the frictional resistance that reduces the tubular articles inside surface, for the face that contacts with the paper on top layer, directly adopts the somatotype layer of existing fluororesin layer, or does not improve.In addition, it is the 3-tier architecture that has 2 layers of structure of polyimide tubulose object and fluororesin somatotype layer or between polyimide layer and fluororesin layer, have bottom, when particularly in the fixing device of Fig. 6, using, owing to be sandwich construction, so thickness is thick, heat conductivity reduces, in addition, its manufacture method also needs 3 kinds of raw materials and 3 different operations, manufacturing process's complexity, and the bonding force of the interlayer that is formed by each material also has problem.
Patent documentation 1: the spy opens flat 7-178741 communique
Patent documentation 2: the spy opens flat 3-25471 communique
Patent documentation 3: the spy opens flat 6-258969 communique
Patent documentation 4: the spy opens flat 11-133776 communique
Patent documentation 5: the spy opens flat 6-23770 communique
Patent documentation 6: the spy opens flat 1-156017 communique
Patent documentation 7: the spy opens flat 2001-341143 communique
Patent documentation 8: the spy opens flat 2001-040102 communique
Patent documentation 9: the spy opens flat 2001-056615 communique
Summary of the invention
The present invention solves the problem of above-mentioned conventional example, a kind of tubular articles and manufacture method thereof are provided, described tubular articles has low friction force at the inside surface of tubular articles, simultaneously, the outside surface of tubular articles also has as the photographic fixing band or adds the sufficient somatotype of pressure zone, the permanance height, cost of manufacture is low.
Tubular articles of the present invention is the tubular articles that the potpourri that contains polyimide and fluororesin particle is formed, is heating and curing and forms, it is characterized in that, near at least a portion fluororesin particle in top layer that is present in above-mentioned tubular articles, separate out in the outside surface of above-mentioned tubular articles or surfaces externally and internally melt-flow, part or whole ground form the fluororesin tunicle.
The manufacture method of tubular articles of the present invention is characterised in that, the mixed solution of the fluororesin particle of polyimide precursor solution and melt-flow is coated on mold outer surface, curtain coating is configured as the thickness of regulation, heat with imidizate, the maximum temperature of above-mentioned imidizate is set at temperature above the fusing point of fluororesin, after the cooling, above-mentioned mould is separated with tubular articles, thus, near the top layer that is present in above-mentioned tubular articles at least a portion fluororesin particle is separated out in the outside surface of above-mentioned tubular articles or surfaces externally and internally melt-flow, and part or whole ground form the fluororesin tunicle.
Description of drawings
Fig. 1 is the summary section of the tubular articles before the imidizate in one embodiment of the present of invention is finished.
Fig. 2 is the summary section of the tubular articles after the imidizate in one embodiment of the present of invention is finished.
The summary section that tunicle when Fig. 3 is the FEP interpolation of representing in one embodiment of the present of invention forms.
Fig. 4 is that FEP and the PTFE of expression in one embodiment of the present of invention mixes the summary section that relatively forms when adding.
Fig. 5 is the sectional view of the curtain coating manufacturing process in expression one embodiment of the present of invention.
Fig. 6 is the summary section of expression by the laser printer fixing device of one embodiment of the present of invention use.
The summary section of Fig. 7 laser printer fixing device that to be expression used by other embodiment of the present invention.
Fig. 8 is the sectional view of the curtain coating manufacturing process among expression other the embodiment of the present invention.
Fig. 9 is the microphotograph of the outside surface of the polyimide tubulose object in the embodiments of the invention 1.
Figure 10 is the microphotograph of the inside surface of the polyimide tubulose object in the embodiments of the invention 1.
Figure 11 is the microphotograph of the outside surface of the polyimide tubulose object in the embodiments of the invention 5.
Figure 12 is the summary section of expression by the determinator of the employed kinetic friction coefficient of one embodiment of the present of invention.
Embodiment
The basis of tubular articles of the present invention is polyimide and fluororesin particle.Polyimide and fluororesin particle do not have intermiscibility, separate out in the outside surface or the fusion of surfaces externally and internally fluororesin of polyimide tubulose object, and the above-mentioned fusion face of separating out form the tunicle that flows on its surface.
And, will contain that the polyimide precursor solution of fluororesin particle that curtain coating forms in the outside surface of mould heats so that during its imidizate, the maximum temperature of imidizate is set at temperature above the fusing point of fluororesin.Thus, the fluororesin particle is separated out in the fusion of outside surface at least of polyimide, can obtain possessing inside surface with low-friction coefficient and the polyimide tubulose object with exterior surface features of high somatotype thus.
Above-mentioned fluororesin is preferably had the granular pattern that is caused by the fluororesin particle by face.This is that a part of fluororesin particle is remaining, observes the surface and is the state of tiny bubble.
Above-mentioned fluororesin particle is preferably selected from least a fluororesin in polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polychlorotrifluoroethylene (PCTFE), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), the tetrafluoroethylene-ethylene copolymer (PETFE).
In order to make the fluororesin of separating out carry out heat flow in the surface of tubular articles, form the fluororesin tunicle, be preferably the thermoplastic fluorocarbon resin of PFA and FEP and so on.These fluororesin can be more than fusing point the temperature current downflow, form at the surfaces externally and internally of tubular articles tunicle as film like.
In addition, as the PTFE resin, even be mixed with the temperature that is heated to more than the fusing point, because melt viscosity height when also being difficult to carry out the fluororesin of heat flow, the state of the surfaces externally and internally of tubular articles is a polyimide with so-called " island structure " that extra large shape exists, the fluororesin particle exists with island.This structure is best suited for being used for the structure of the purposes such as intermediate transfer belt of image processing system.Promptly, above-mentioned transfer belt is in order to make the toner picture carry out intermediateness ground transfer printing from photoreceptor, the band that then the toner picture is needed on copy paper again and uses, after being needed on copy paper again, the toner powder that remains in the transfer belt surface on a small quantity scraped with scraper plate get when removing, and the sliding resistance between the scraper plate is low, is preferred construction.
The polyimide that uses among the present invention is a heat-curing resin, the mixed solution curtain coating of polyimide precursor solution and fluororesin can be formed in for example outside surface or the inside surface of mould, carry out drying and heating to finish imidizate, can be produced on the outside surface at least of tubular articles or the polyimide that the surfaces externally and internally fluororesin is separated out/fluororesin composite tube object.
The tubular articles of making of said method, on its tunicle and face that air contacts, the easy fusion of fluororesin is separated out.That is, fluororesin powder exists with the state that mixes and disperse in polyimide precursor solution.But, it has been generally acknowledged that, utilizing heat treated to carry out in the process of imidizate, by the temperature of heat treated to the fusing point that surpasses fluororesin, thus, fusion fluororesin move towards the outermost layer that contacts with air at the thickness direction of tubular articles.
The detailed mechanism of fluororesin mobile phenomenon in above-mentioned tubular articles is also indeterminate, but present inventors have carried out a lot of experiments and research continuously, found that, with the mixed solution curtain coating of above-mentioned polyimide precursor solution and fluororesin on glass plate, carrying out curtain coating is shaped, carry out drying and heating to finish imidizate, in the making of polyimide/fluororesin laminated film, on above-mentioned film and face that glass contacts, fluororesin also fusion is separated out, and has carried out confirming experiment in tubular articles of the present invention.
It found that, also can separate out fluororesin at the inside surface of the tubular articles that does not contact with air layer fully.Find that in addition the phenomenon of separating out fluororesin on the two sides of tubular articles is because of the difference of fluororesin kind or the temperature difference difference of imidizate operation.
That is, the phenomenon separated out of fluororesin is subjected to the imidizate Temperature Influence of the fusing point and the polyimide precursor of fluororesin.In the detailed experiments result, when using biphenyl tetracarboxylic dianhydride (BPDA) to be mixed with fluororesin in the polyimide as the rigidity of aromatic diamine as aromatic tetracarboxylic acid's dianhydride and p-phenylenediamine (PPD) (PPD), if the maximum temperature of imidizate is lower than the fusing point of fluororesin, then fluororesin manifests on any face of tubular articles all not obviously, when the raising temperature is above to the fusing point of fluororesin, in the two sides fluororesin fusion of the inside surface of tubular articles, outside surface, separate out, can obtain having the tubular articles of low frictional resistance.
Find in addition, the polyimide precursor solution monomer that is made of above-mentioned aromatic tetracarboxylic acid's dianhydride and aromatic diamine is carried out imidizate and the percent thermal shrinkage of the polyimide that obtains is big, help making the fluororesin fusion to be separated out.That is to say, with polyimide precursor solution curtain coating on the glass plate be shaped and drying after, be heated to 300 ℃ interimly, make it carry out imidizate, then, after the cooling Kapton is peeled off from glass plate, the big polyimide of the percent thermal shrinkage that temperature more than 300 ℃ of fusing points that are heated to fluororesin for example obtains 400 ℃ the time, the easy fusion of fluororesin is separated out.
The result of above-mentioned test is, from by being 0.9% as the BPDA of aromatic tetracarboxylic acid's two anhydride components with as the percent thermal shrinkage that the polyimide precursor that the PPD of aromatic diamine composition constitutes is made the film that obtains, the percent thermal shrinkage of the film that obtains from the polyimide precursor that uses PMDA and ODA is 0.09%.The relation of the phenomenon that the value of the percent thermal shrinkage of Kapton and fluororesin fusion are separated out is: found that the percent thermal shrinkage in 300 ℃～400 ℃ is big more, the easy more phenomenon of separating out from the polyimide tunicle of fluororesin.
DCO method to above-mentioned percent thermal shrinkage describes below.The mensuration of percent thermal shrinkage is used " TMA-50 " of society of Shimadzu Seisakusho Ltd. system.The following making of Kapton: the polyimide precursor solution curtain coating that will be obtained by above-mentioned monomer is on glass plate, thickness when imidizate is finished is 50 μ m, after under 150 ℃ the temperature dry 40 minutes, heated 40 minutes down at 200 ℃, further heated 20 minutes down at 250 ℃, heated 20 minutes down at 300 ℃, make Kapton.
It is that 10mm, width are the oblong-shaped of 3.5mm that this film is cut into length, in its loading that simultaneously applies 2.0g, is installed on " TMA-50 ".Observe the state of its thermal shrinkage from room temperature to 400 ℃ with 10 ℃/minute programming rate, calculate the percent thermal shrinkage in 300 ℃～400 ℃.
In addition, utilization has used the polyimide precursor solution than the low-melting FEP of PTFE (fusing point: 327 ℃) (fusing point: 250 ℃) to experimentize, consequently, the maximum temperature of imidizate is 300 ℃ a temperature, fluororesin (FEP) is separated out at the surfaces externally and internally of tubular articles, and heat flow is carried out on its surface, forms the state of tunicle, can obtain having the tubular articles of low frictional resistance.
As mentioned above, about separate out the phenomenon of fluororesin at the surfaces externally and internally of tubular articles of the present invention, by the fusing point of selected fluororesin, the imidizate temperature of polyimide precursor etc., and be set at defined terms, can fluororesin separated out.
Tubular articles of the present invention can be an individual layer, also can be formed by multilayer as required.Under the situation of multilayer, internal layer also can not contain the fluororesin particle or than its amount ground shaping polyimide layer of outer relative minimizing, can further improve the mechanical property of tubular articles.In addition, also can make multilayer by the kind of polyimide or fluororesin or the different layer of combined amount of fluororesin.And, also can use the polyimide precursor curtain coating in mould that is mixed with fluororesin to be shaped after, the temperature during the control imide reaction, only the outside surface at tubular articles is separated out the fluororesin fusion.This is only to make it have the situation that good rubbing characteristics gets final product on outer field surface because also exist as purposes such as intermediate transfer belt.
In addition, mix in the polyimide precursor solution at above-mentioned fluororesin, can add heat conductivity fillers such as boron nitride, potassium titanate, mica, titanium dioxide, talcum, lime carbonate, aluminium nitride, aluminium oxide, silit, silicon, silicon nitride, silica, graphite, carbon fiber, metal powder, beryllia, magnesium, magnesium oxide etc.By adding these heat conductivity fillers, can improve the heat conductivity of tubular articles tunicle, and adapt with the high speed photographic fixing, be preferred.
In the present invention, above-mentioned fluororesin can use PTFE, PFA, fluororesin such as FEP, CPTFE with the form of monomer, or mixes and use.PTFE, PFA, FEP thermotolerance, somatotype are good, are the preferable material that can use in the present invention.In addition, in being mixed with the polyimide precursor solution of above-mentioned fluororesin, can add conductive material or antistatic agent such as carbon black, carbon fiber, metal powder.
Becoming the state of ghost image on reduction by use mixing the fluororesin that is dispersed with electric conductivity or antistatic agent, can improve the image quality that is caused by static set-off etc. that produces in image formation process or the image, is preferred.
In addition, to be preferably set to the solid constituent with respect to polyimide precursor solution be 10～90 quality % to the combined amount of above-mentioned fluororesin.Preferred especially 20～80 quality %.
When the content of above-mentioned fluororesin is lower than 10 quality %, has the tendency that fluororesin is few and effect reduction frictional resistance tails off that fusion is separated out, in addition, when it surpassed 90 quality %, the flatness with physical strength step-down and tubular articles surface was also impaired, be easy to generate the tendency of breaking.
In addition, above-mentioned fluororesin is the easy form of mixing of powdered substance preferably, and preferred mean grain size is the scope of 0.1～100 μ m.Preferred mean grain size is the scope of 0.5～50 μ m.Since when its in such scope the time, the cohesion of particle is few, can disperse equably, so be preferred.
In addition, because when above-mentioned mean grain size is lower than 0.1 μ m, particle carries out secondary aggregation easily, when it surpasses 100 μ m, the inside surface of tubular articles or outside surface be easy to generate by the fluororesin particle cause concavo-convex, so not preferred.In addition, the assay method of the mean grain size of above-mentioned fluororesin powder can with laser diffraction formula granulometry device (ASLD-2100: society of Shimadzu Seisakusho Ltd. system) or laser diffraction/diffuse transmission type particle size distribution device (LA-920: the hole field makes society of institute system) measure.
In order to adjust the size of above-mentioned fluororesin particle, before the mixed solution with polyimide precursor solution and fluororesin particle is coated on mold outer surface, preferably above-mentioned mixed solution is filtered with filtrator, remove the oversize grain of fluororesin particle.
In addition, tubular articles of the present invention is to be the tubular articles of principal ingredient with the polyimide, is after fluororesin and polyimide precursor solution being mixed, curtain coating is configured as seamless shape, adds hot-imide and obtains.Above-mentioned polyimide precursor solution can make roughly equimolar aromatic tetracarboxylic acid's dianhydride and aromatic diamine react in organic polar solvent and obtain.
As the typical example of above-mentioned aromatic tetracarboxylic acid's dianhydride, can list 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, pyromellitic acid dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 2,2 '-two (3,4-dicarboxyl phenyl) propane dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride etc.
In addition, typical example as above-mentioned aromatic diamine, can list 4,4 '-diamino-diphenyl ether, p-phenylenediamine (PPD), m-phenylene diamine, 1, the 5-diaminonaphthalene, 3,3 '-dichloro-benzidine, 3,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diamido diphenyl sulfide-3,3 '-diamino diphenyl sulfone, biphenylamine, 3,3 '-dimethylbenzidine, 4,4 '-diamino-phenyl sulfone, 4,4 '-diamino-diphenyl propane, MXDP, hexamethylene diamine, diamido propyl group tetra-methylenedimine, 3-methylheptyl methylene diamine etc.
These aromatic tetracarboxylic acid's dianhydrides and aromatic diamine can be used alone or as a mixture.In addition, it is finished to polyimide precursor solution, these precursor is mixed and use.
In the combination of above-mentioned aromatic tetracarboxylic acid's dianhydride and aromatic diamine, the combination of preferred biphenyl tetracarboxylic dianhydride and p-phenylenediamine (PPD).By the polyimide that this precursor obtains, the structure of polymkeric substance is a rigidity, becomes the structure that easily fluororesin is expressed into the outside under the melt temperature of fluororesin.
As the organic polar solvent that makes the reaction of above-mentioned aromatic tetracarboxylic acid's dianhydride and aromatic diamine, can list N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, N, N-dimethyl acetamide, N, N-diethylformamide, N, N-diethyl acetamide, dimethyl sulfoxide, HMPA, pyridine, dimethyl tetramethylene sulfone, tetramethylene sulfone etc.These organic polar solvents also can mix phenol, dimethylbenzene, hexane, toluene etc.
Above-mentioned polyimide precursor solution is by above-mentioned aromatic tetracarboxylic acid's dianhydride and aromatic diamine are obtained in reaction below 90 ℃ usually, solid component concentration in the solvent can be set according to the specification or the processing conditions of final polyimide tubulose object, is 10～30 quality %.
In addition, when in organic polar solvent, making aromatic tetracarboxylic acid's dianhydride and aromatic diamine when reaction, rise, can dilute in use for the viscosity of regulation and use according to the viscosity of its polymerization situation solution.According to creating conditions or operating conditions, use with the viscosity of 1～5000 pool usually.
In manufacture method of the present invention, the temperature for the outside surface at least at tubular articles can make fluororesin layer separate out need be heated to the temperature above the fusing point of fluororesin.The maximum temperature of imidizate is preferably under the high temperature more than 10 ℃ of fusing point than the fluororesin that mixes and finishes imidizate.
In addition, for making fluororesin separate out needed heat time heating time for the surfaces externally and internally at above-mentioned tubular articles, the maximum temperature that is preferably imidizate arrive to surpass after the temperature of fusing point of fluororesin 30 minutes with the interior time.When it was time more than 30 minutes, the thermal decomposition of fluororesin or the mechanical property of polyimide might reduce.
Tubular articles of the present invention for example can obtain by the following method.Die surface coating fluororesin at the external diameter of stipulating (footpath that is equivalent to the internal diameter of tubular articles) mixes polyimide precursor solution, use mold (dies) to carry out curtain coating is shaped in the outside, import heating arrangement, under 100～150 ℃ lower temperature, make the polymer solvent drying, then, carry out imidization reaction, finally under the temperature of the fusing point that surpasses fluororesin, heat the stipulated time to finish imidizate.Cool off then, tubular articles is taken off from above-mentioned mould.
In one embodiment of the invention, with fluororesin (PTFE) powder in polyimide precursor solution, the summary amplification profile of curtain coating is shaped, the temperature of the imidizate of polyimide obtains when being 300 ℃ tubular articles 10 is illustrated in Fig. 1.Till this stage, fluororesin powder 12 is dispersed in the inside of polyimide film layer 11, and top layer face major part is covered by polyimide layer.Contact angle at this stage water is also low.The 15th, mould.
Then, when the imidizate temperature was set at 400 ℃, as shown in Figure 2, the fluororesin powder fusion was separated out in the air side surface layer in the mode of oozing out from polyimide surface.The 13rd, fusion and the fluororesin that oozes out.The 14th, fusion is separated out in the fluororesin of the inner surface side of die side.When it was this state, the contact angle of water raise.Fluororesin with the relation of polyimide in, be non-ly to mix and be island structure (sea is a polyimide, and the island is a fluororesin), and, fusion fluororesin partly separate out from polyimide surface.
Fig. 3 only mixes FEP (fusing point is 260 ℃) particle separately and carries out curtain coating to be shaped in polyimide precursor solution, the summary amplification profile of the tubular articles that obtains when the imidizate temperature of polyimide is set at 400 ℃.FEP powder 22 is dispersed in the inside of polyimide film layer 21, FEP melt-flow and separating out at the extexine face, part or whole ground form fluororesin tunicle 23.The 30th, the resin in the FEP of inside surface is separated out in fusion.The 28th, mould.
Fig. 4 mixes PTFE (fusing point is 327 ℃) particle and FEP (fusing point is 260 ℃) particle and carries out curtain coating with 50: 50 ratio to be shaped in polyimide precursor solution, the summary amplification profile of the tubular articles when the imidizate temperature of polyimide is set at 400 ℃.Be dispersed with FEP powder 22 and PTFE powder 24 in the inside of polyimide film layer 21, FEP and PTFE melt-flow and separate out at the top layer face, part or whole ground form fluororesin tunicle (23,25).The 28th, mould.
In the present invention, owing near at least a portion fluororesin particle the top layer that is present in tubular articles is separated out in the outside surface or the surfaces externally and internally fusion of tubular articles, the fluororesin that this fusion is separated out carries out polyimideization and integrated, and form mobile tunicle at above-mentioned tubulose body surface, therefore, the kinetic friction coefficient of tubular articles inside surface is low, in addition, because the outside surface of tubular articles is also formed by the fluororesin tunicle, therefore, fusion the somatotype of toner also high, do not need as existing photographic fixing band, fluororesin somatotype layer to be shaped again yet, can be used for the fixing member of image processing system or transfer belt or the intermediate transfer heat fixer band etc. of holding concurrently with other operation.And, the mixed solution that will be added with the fluororesin particle in polyimide precursor solution is coated on shaping dies outside surface or inside surface, curtain coating is configured as the thickness of regulation, heat with imidizate, the maximum temperature of above-mentioned imidizate is set at temperature above the fusing point of fluororesin, thus, near at least a portion fluororesin pellet melting that is present in the top layer of tubular articles can be separated out in the outside surface at least of tubular articles.Has the shaping thing of separating out the structure of fluororesin in the one or both sides fusion of polyimide base material, under the situation of film like, can be suitable as heat-resisting sliding material or somatotype film, perhaps make tube shape, also go for being fit to having the chemical stability of fluororesin and the mechanical property of polyimide etc. medical field conduit or insert medical various pipes in the body etc.
Embodiment
Below, illustrate in greater detail the present invention based on embodiment.Need to prove that the present invention is not limited to following embodiment.
In following embodiment and comparative example, the biphenyl tetracarboxylic dianhydride brief note is " BPDA ", and the p-phenylenediamine (PPD) brief note is " PPD ", the pyromellitic acid dianhydride brief note is " PMDA ", 4,4 '-diamino-diphenyl ether brief note is " ODA ", and N-N-methyl-2-2-pyrrolidone N-brief note is " NMP ".
In addition, the contact angle to pure water of the kinetic friction coefficient of the tubular articles that is obtained by the present invention and the film that obtained by these materials is measured with following method.
(1) assay method of kinetic friction coefficient (being shown in Figure 12)
The mensuration of kinetic friction coefficient is carried out according to JISK7125.Being fixed with width on the desk 64 of level is that 80mm, length are the test film 62 of 200mm size.Overlapping above it width is that 63mm, length are that (area is 40cm to 63mm
2) size and be the test film 61 of identical material with fixing test film 62, further placing width above it is that 63mm, length are that (area is 40cm to 63mm
2), weight is the weight 63 of 200g, and the speed along continuous straight runs of overlapping test film with 100mm/ minute slided, and measures its loading (kinetic force of friction), utilizes following formula to calculate kinetic friction coefficient.Represent that with 65 metal wire, 66 represents that coaster, 67 represents the force cell of cupping machine (load cell) and roll along the Z direction.
Kinetic friction coefficient μ
D=F
D/ F
P
F
D: kinetic force of friction (N)
F
P: the normal force that produces by the quality of slide (=1.96N)
(2) measurement of contact angle
Use " FACE CA-Z " analyzer of consonance surface chemistry Co., Ltd. system, mensuration is to the contact angle of 23 ℃ pure water.
(embodiment 1)
(1) fluororesin mixes the making of polyimide precursor solution
With respect to 100 mass parts BPDA, in flask, 39 mass parts PPD are dissolved in NMP (monomer concentration 18.2 quality %), stirred 6 hours under 23 ℃ temperature on one side, makes its reaction on one side, obtains polyimide precursor solution.The rotary viscosity of this polyimide precursor solution is 1200 pools.Need to prove that rotary viscosity is the value of measuring with Brookfield viscometer under 23 ℃ of temperature.Then, (fusing point is 327 ℃: the Dupont corporate system to add mean grain size and be the PTFE powder of 3.0 μ m in above-mentioned polyimide precursor solution, commodity are called " Zonyl MP1100 ") and stir, so that it is the ratio of 20 quality % with respect to the solid constituent in the polyimide precursor solution, (fusing point is 260 ℃ to the FEP powder that further interpolation mean grain size is 35 μ m: the Dupont corporate system, trade name " 532-8110 "), so that it is the ratio of 4.0 quality % with respect to the solid constituent in the polyimide precursor solution, and stir, it is disperseed equably.Then, use the stainless steel wire mesh of 250 orders (mesh) that thick foreign matter is filtered, prepared fluororesin powder and mixed polyimide precursor solution.
(2) making of tubular articles
At external diameter is that 24mm, length are that the surface of the aluminium-making mould of 500mm utilizes dip coating coating monox coating agent and sintering, capping oxidation silicon fiml.
Then, as shown in Figure 5, the part of mould 1 from front end to 400mm is immersed in above-mentioned fluororesin powder mixes the polyimide precursor solution 4, after the coating, inserting internal diameter from the top of above-mentioned mould is the ring-type mold 2 of 25mm, and move it, form the casting films 3 of the thickness of 500 μ m on the surface of above-mentioned mould.
Then, put into 120 ℃ baking oven together with above-mentioned mould 1, after dry 60 minutes, make its temperature that is warming up to 200 ℃ with 40 minutes, maintenance is 20 minutes under uniform temp, finally handle in heating under 250 ℃ the temperature after 10 minutes as imidizate, with the temperature that was warming up to 400 ℃ in 15 minutes, heating was cooled to room temperature (25 ℃) to finish imidizate in 10 minutes under uniform temp, then, tubular articles is taken off from mould.
The thickness of the tubular articles that obtains is 55 μ m, and both ends are cut, and obtaining length is that 240mm (A4 size), internal diameter are the tubular articles of 24mm.
The measurement result of the kinetic friction coefficient of the surfaces externally and internally of this tubular articles is shown in the table 1 of back.In addition, will utilize the observation photo of 1000 times outside surface of digital microscope (VHX-100 of Keyence corporate system) observation to be shown in Fig. 9.The hickie point-like visible part of outside surface is the PTFE resin particle, and the part that the state to flow around it is separated out is the FEP resin.Can confirm that fluororesin tunicle mask as a whole has the granular pattern that is caused by the fluororesin particle.In addition, the same photo with the inside surface of this tubular articles is shown in Figure 10.Blackspot point-like visible part is the part that the PTFE resin is separated out, and white visible part on every side is the fusion of FEP resin and mobile part.
With this polyimide tubulose object as per minute shown in Figure 6 can photographic fixing 10 the photographic fixing of laser printer bring installation, carry out image fixing, consequently obtained preferable image.
(comparative example 1)
Under the condition of embodiment 1, in polyimide precursor solution, do not mix fluororesin powder, in addition, under condition similarly to Example 1, obtain polyimide tubulose object.The measurement result of the kinetic friction coefficient of the inside surface of this tubular articles is shown in table 1.
(embodiment 2)
In the polyimide precursor monomer solution that the BPDA/PPD that is worked good by embodiment 1 constitutes, only add as the mean grain size of fluororesin powder and be the FEP powder (Dupont corporate system, trade name " 532-8110 ") of 35 μ m and mix, so that it is the ratio of 23 quality % with respect to the solid constituent in the polyimide precursor solution, has prepared fluororesin and mixed polyimide precursor solution.
Then, similarly to Example 1 at die surface coating polyimide precursor solution, carrying out curtain coating is shaped, implementing imidizate similarly to Example 1 handles, finally handle, made it be warming up to 300 ℃ temperature with 5 minutes after 10 minutes in heating under 250 ℃ the temperature as imidizate, heating is 15 minutes and cool off under 350 ℃ temperature, obtains polyimide tubulose object.
The measurement result of the kinetic friction coefficient of this tubular articles is shown in table 1.In addition, as per minute shown in Figure 6 can photographic fixing 10 the photographic fixing of laser printer bring installation, carry out image fixing, consequently obtained preferable image.In Fig. 6, the 31st, photographic fixing band (polyimide tubulose object), the 32nd, tape guide, the 33rd, ceramic heater, the 34th, have the backer roll of drive source, the 35th, thermistor(-ter), the 36th, the plug of backer roll, the 37th, copy paper, the 38th, the toner picture before the photographic fixing, the 39th, the toner picture after the photographic fixing, N is a bite.
(embodiment 3)
In the polyimide precursor monomer solution that the BPDA/PPD that is worked good by embodiment 1 constitutes, only add as the mean grain size of fluororesin powder and be the PFA powder (Dupont-MitsuiFluorochemicals corporate system, commodity PFAMP102 by name) of 28 μ m and mix, so that it is the ratio of 24 quality % with respect to the solid constituent in the polyimide precursor solution, has prepared fluororesin and mixed polyimide precursor solution.
Then, similarly to Example 1 the die surface polyimide precursor solution is carried out curtain coating and be shaped, the maximum temperature that makes polyimideization under condition similarly to Example 1 is 400 ℃ to be handled, and obtains polyimide tubulose object.Wherein, above-mentioned mould uses the mould of external diameter as 30mm.
The measurement result of the kinetic friction coefficient of this tubular articles is shown in table 1.In addition, as per minute shown in Figure 7 can photographic fixing 6 the pressurization of laser printer bring installation, carry out image fixing, consequently obtained preferable image.In Fig. 7, the 51st, add pressure zone, the 52nd, push guide piece, the 53rd, push liner, the 54th, fixing roller, the 55th, thermal source, the 56th, the toner picture before the photographic fixing, the 57th, copy paper.
(embodiment 4)
With respect to 100 mass parts PMDA, in flask, 75 mass parts ODA are dissolved in NMP (monomer concentration 18.0 quality %), stirred 6 hours under 23 ℃ temperature on one side, makes its reaction on one side, obtains polyimide precursor solution.The rotary viscosity of this polyimide precursor solution is 1500 pools.Rotary viscosity is the value of measuring with Brookfield viscometer under 23 ℃ of temperature.Then, only to add mean grain size be the FEP powder (fusing point is 270 ℃: Dupont corporate system, trade name " 532-8110 ") of 35 μ m and mix, so that it is the ratio of 26 quality % with respect to the solid constituent in the polyimide precursor solution, has prepared fluororesin and mixed polyimide precursor solution.
Then, on the surface of mould polyimide precursor solution is carried out aqueous shaping similarly to Example 1.Then, drying is 60 minutes in 120 ℃ baking oven, be warming up to 200 ℃ with 20 minutes, heating is 20 minutes under uniform temp, finally handle in heating under 250 ℃ the temperature after 10 minutes as imidizate, with the temperature that was warming up to 400 ℃ in 10 minutes, heating is 10 minutes under 400 ℃ temperature, cool off, obtain polyimide tubulose object.
The measurement result of the kinetic friction coefficient of this tubular articles is shown in table 1.In addition, as per minute shown in Figure 6 can photographic fixing 6 the photographic fixing of laser printer bring installation, carry out image fixing, consequently obtained preferable image.
(comparative example 2)
Under the condition of embodiment 1, final imidizate temperature is changed to 250 ℃, in addition, under condition similarly to Example 1, obtain polyimide tubulose object.The measurement result of the kinetic friction coefficient of the inside surface of this tubular articles is shown in table 1.
It is square (vertical: 300mm, horizontal stroke: on glass plate 300mm) to be formed in 300mm by the fluororesin mixing polyimide precursor solution curtain coating that each embodiment and comparative example modulate, so that it becomes the thickness of 80 μ m, under the highest imidizate temperature of table 1, finish imidizate, obtain Kapton.Then, each film be the results are shown in table 1 to the measurement of contact angle of pure water.
(embodiment 5)
Use the building mortion of the tubular articles shown in the table 8, the slit 70 that spues of the discharge opening of the polyimide precursor that the internal diameter that will have the slotted section 72 that spues is 230.2mm, the gap opening width that spues is 1.4mm is installed in the above-mentioned building mortion.In addition, the preparation external diameter is that 229mm, length are that the aluminium-making mould of 500mm is as shaping dies 71, use utilizes infusion process that the monox coating agent is coated on the mould that die surface and sintering, oxidized silicon fiml cover, and the mode that enters the inboard of the slit portion that spues with the upper end of mould is provided with.The average surface rugosity (Rz) of above-mentioned mould is 2.2 μ m.
Then, adding mean grain size in the polyimide precursor monomer solution that the BPDA/PPD that is worked good by embodiment 1 constitutes is the PTFE powder (fusing point is 327 ℃: Dupont corporate system, trade name " Zonyl MP1100 ") of 3.0 μ m, so that it is the ratio of 23 quality % with respect to the solid constituent in the polyimide precursor solution, and stirring disperses it equably.Then, use 250 purpose stainless steel wire meshes, thick foreign matter is filtered, prepared PTFE powder polyimide precursor solution.
Then, in above-mentioned PTFE powder polyimide precursor solution, further add acidic black (Mitsubishi chemical Co., Ltd's system, trade name " MA78 ", DBP uptake: 70cm
3, per unit specific surface area 100m
2The volatile ingredient of/g: 2.6 weight %), making it is 14.5 quality % with respect to polyimide resin, makes to make polyimide, PTFE and 3 kinds of compositions of carbon black mix the polyimide precursor solution of disperseing.
Then, above-mentioned PTFE mixing precursor solution 74 is dropped into storage tank 73, make mashing pump 77 rotations, with dividing cell 78 polyimide precursor solution of ormal weight is allocated in 24 places, use pipe arrangement 79,80 (other pipe arrangement not have to illustrate) to be connected with the pipe arrangement connector in the slit 70 that spues, force feed is to the gap opening portion that spues.Simultaneously, direction along arrow Y makes the mould vertical uplift, when mould 71 from the position of the downward 50mm of topmost by the moment of the slit portion that spues, from mashing pump 77 force feed polyimide precursor solution, polyimide precursor solution 81 curtain coatings are shaped at the outside surface of mould 71 thickness with 600 μ m.The 75th, liquid pushing tube, the 76th, valve.The force feed speed of mashing pump 77 and the ascending velocity of mould 71 are calculated by data such as the viscosity of polyimide precursor solution, the external diameter of mould 71, aqueous forming thicknesses in advance by experiment, set defined terms.Mould 71 begin the moment of the position of 50mm from foot by the slit portion that spues, stop force feed from mashing pump, finish aqueous shaping on the surface of mould 71 with the length of about 400mm.Then, above-mentioned mould is directly put into baking oven, at 120 ℃ down after dry 60 minutes, make its temperature that is warming up to 200 ℃ with 40 minutes, maintenance is 20 minutes under uniform temp.Then, make it be warming up to 300 ℃ with 20 minutes, and kept 30 minutes, further be warming up to 340 ℃ with 15 minutes, under uniform temp heating 20 minutes with after finishing imidizate, from baking oven take out and cooling after, from the mould off-type, make polyimide tubulose object.
The thickness of this tubular articles is 57 μ m, and the specific insulation when applying voltage 500v is 1.1 * 10
8Ω cm.In addition, the surfaces externally and internally in tubular articles is separated out in the above-mentioned PTFE resin fusion that mixes in precursor solution, in the data of kinetic friction coefficient, has obtained the result that outside surface is Duoed than separating out of inside surface.
To this tubular articles, will utilize the photo of 1000 times outside surface of digital microscope (Keyence corporate system VHX-100) observation to be shown in Figure 11.Can confirm that hickie point-like visible part is the PTFE resin particle, has the granular pattern that is caused by the fluororesin particle.
The kinetic friction coefficient and the measurement of contact angle of this tubular articles be the results are shown in table 1.Use the intermediate transfer belt of this tubular articles as the tandem laser printer of full color, consequently, after the color toner that will be formed at belt surface looks like to be needed on copy paper, when the chemglaze system scraper plate of utilization is removed the toner that remains on the transfer belt, the sliding resistance on above-mentioned scraper plate and transfer belt surface is low, remaining toner be can remove reliably, distinct image and sufficient permanance obtained.In addition, since few separating out of the fluororesin of the inside surface of above-mentioned tubular articles, therefore between the driven roller of the inside surface that is disposed at transfer belt, can not transmit reliable rotation slidably, and the toner picture can be disorderly, can prevent image blurring generation.The volume resistance rate is the method according to JISC2151, and the digital superelevation resistance/micro current instrument R8340/R8340A that uses ア De バ Application テ ス ト society system is to measure in 30 seconds with application time.
(embodiment 6)
(1) making of the 1st of the sandwich construction tubular articles the layer (internal layer)
In the polyimide precursor monomer solution that the BPDA/PPD that is prepared by embodiment 1 constitutes, (MBN-010T of Mitsui Chemicals, Inc) mixes with boron nitride powder, so that its solid component concentration with respect to above-mentioned polyimide precursor solution is 30 quality %, makes boron nitride powder and mix polyimide precursor solution.Then, the surface use ring-type mold of the mould that uses in embodiment 1 applies, curtain coating is shaped, so that be 35 μ m by film thickness behind the imidizate, after 120 ℃ of following dryings, carry out the intermediate treatment of imidizate under 250 ℃ temperature, the 1st layer the tunicle that carries out the tubular articles that is made of the polyimide tunicle that is mixed with boron nitride powder is shaped.
(2) be used for the making of polyimide precursor solution of the 2nd layer (skin) of sandwich construction tubular articles
In the polyimide precursor monomer solution that the BPDA/PPD that is prepared by embodiment 1 constitutes, SUMMITPRECISION POLYMERS CORPORATION system " SP-Powdered PTFE ") and carbon fiber (clear with Electricity worker society system " VGCF-H ") add PTFE powder (327 ℃ of the fusing points: of mean grain size 3.0 μ m, making the PTFE powder is the ratio of 70 quality % with respect to the solid component concentration in the polyimide precursor solution, carbon fiber is the ratio of 5 quality % with respect to the solid component concentration in the polyimide precursor solution, and stir, it is disperseed equably.Then, use 250 purpose stainless steel wire meshes, thick foreign matter is filtered, prepared fluororesin powder and carbon fiber and mixed polyimide precursor solution.
(3) the 2nd of the sandwich construction tubular articles the layer of shaping of (skin) and finishing of imidizate
Use the ring-type mold, the 1st layer the tubular articles surface of in above-mentioned (1) item, making, the fluororesin powder and the carbon fiber of above-mentioned (2) preparation are mixed the shaping of polyimide precursor solution curtain coating, so that be 20 μ m by film thickness behind the imidizate, after carrying out drying under 120 ℃ the temperature, carrying out an imidizate under 250 ℃ temperature handles, further with the temperature that was warming up to 400 ℃ in 15 minutes, heating obtained having the polyimide tubulose object of internal layer that is mixed with boron nitride powder in polyimide and the outer field 2 layers of structure that are mixed with fluororesin powder and carbon fiber in the same manner in polyimide to finish imidizate in 20 minutes under uniform temp.The internal diameter of this tubular articles is 24mm, and gross thickness is 54 μ m, and layers 1 and 2 can not be peeled off by imidizate and firmly bonding.In addition, at the outside surface of tubular articles, the fluororesin fusion that has mixed is separated out, and has the good somatotype of fluororesin and a low rubbing characteristics.The measurement result of the kinetic friction coefficient of the surfaces externally and internally of this tubular articles is shown in table 1.This tubular articles is by layers 1 and 2 is carried out imidizate and the integrated structure that forms, the 1st layer (internal layer) has the mechanical property that needs as tubular articles, there are a large amount of fluororesin fusions that mixed separate out in the 2nd layer (skin), can obtain the somatotype layer of abundant thickness, obtain good permanance.
In addition, by boron nitride that in the 1st layer, mixes and the carbon fiber that in the 2nd layer, mixes, can improve the heat conductivity of the thickness direction of tubular articles, separating out in the surface resistance of outermost fluororesin layer simultaneously is 800 Ω/, as per minute can photographic fixing 14 the photographic fixing of laser printer as shown in Figure 6 bring installation, carry out image fixing, consequently do not have set-off to occur yet, obtained preferable image.
(embodiment 7)
(1) making of the 1st of the sandwich construction tubular articles the layer (internal layer)
In the polyimide precursor monomer solution that the BPDA/PPD that is prepared by embodiment 1 constitutes, with mean grain size is that PTFE powder (fusing point is 327 ℃: Dupont corporate system, trade name " Zonyl MP1100 ") the 15 quality % of 3.0 μ m mix, and has cooperated the mixed solution of fluororesin and polyimide precursor.Then, the surface of the mould that uses at embodiment 3 uses that the ring-type mold applies, curtain coating is shaped, so that be 35 μ m by film thickness behind the imidizate, after 120 ℃ of following dryings, under 250 ℃ temperature, carry out the intermediate treatment of imidizate, be configured as the 1st layer the tunicle that constitutes by above-mentioned mixed solution.
(2) be used for the making of polyimide precursor solution of the 2nd layer (skin) of sandwich construction tubular articles
In the polyimide precursor monomer solution that the BPDA/PPD that embodiment 1 prepares constitutes, SUMMITPRECISION POLYMERS CORPORATION system " SP-Powdered PTFE ") and carbon fiber (clear with Electricity worker society system " VGCF-H ") (fusing point is 327 ℃: to add mean grain size and be the PTFE powder of 3.0 μ m, making the PTFE powder is the ratio of 55 quality % with respect to the solid component concentration in the polyimide precursor solution, carbon fiber is the ratio of 5 quality % with respect to the solid component concentration in the polyimide precursor solution, and stir, it is disperseed equably.Then, use 250 purpose stainless steel wire meshes, thick foreign matter is filtered, prepared fluororesin powder and carbon fiber and mixed polyimide precursor solution.
(3) the 2nd of the sandwich construction tubular articles the layer of shaping of (skin) and finishing of imidizate
Use the ring-type mold, on the 1st layer the tubular articles surface that above-mentioned (1) item is made, above-mentioned (2) fluororesin powder that mixes and carbon fiber are mixed the shaping of polyimide precursor solution curtain coating, so that be 20 μ m by film thickness behind the imidizate, after carrying out drying under 120 ℃ the temperature, carrying out an imidizate under 250 ℃ temperature handles, further with the temperature that was warming up to 400 ℃ in 15 minutes, heating obtained having the polyimide tubulose object of internal layer that is mixed with fluororesin in polyimide and the outer field 2 layers of structure that are mixed with fluororesin powder and carbon fiber in the same manner in polyimide to finish imidizate in 20 minutes under uniform temp.The internal diameter of this tubular articles is 24mm, and gross thickness is 55 μ m, and layers 1 and 2 is by imidizate and firmly bonding.In addition, at the outside surface and the inside surface of tubular articles, fluororesin fusion and separating out has the good somatotype of fluororesin and low rubbing characteristics.The measurement result of the kinetic friction coefficient of the surfaces externally and internally of this tubular articles is shown in table 1.The skin resistance of the fluororesin layer of separating out at the outermost layer of this tubular articles is 815 Ω/, the pressure zone that adds as the laser printer that fixing device shown in Figure 7 is installed uses, and carries out image fixing, consequently, do not have set-off to occur yet, obtained preferable image.
[table 1]
| Embodiment | Acid composition/the amine component of polyimide | Fluororesin/fusing point (℃) | Maximum temperature imidizate temperature (℃) | Kinetic friction Resistance Value outside surface (N) | Kinetic friction Resistance Value inside surface (N) | The contact angle outside surface (°) | The contact angle inside surface (°) | |
| |
BPDA/PPD | PTFE/327℃ | FEP/260℃ | 400 | 0.09 | 0.09 | 108 | 106 |
| |
BPDA/PPD | - | FEP/260℃ | 350 | 0.08 | 0.11 | 101 | 96 |
| Embodiment 3 | BPDA/PPD | - | PFA/300℃ | 400 | 0.09 | 0.10 | 103 | 105 |
| Embodiment 4 | PMDA/ODA | - | FEP/260℃ | 400 | 0.08 | 0.10 | 103 | 100 |
| Embodiment 5 | BPDA/PPD | PTFE/327℃ | - | 340 | 0.16 | 0.20 | 98 | 85 |
| Embodiment 6 | BPDA/PPD | PTFE/327℃ | - | 400 | 0.08 | 0.38 | 108 | 74 |
| Embodiment 7 | BPDA/PPD | PTFE/327℃ | - | 400 | 0.08 | 0.13 | 105 | 95 |
| Comparative example 1 | BPDA/PPD | - | - | 400 | 0.40 | 0.40 | 70 | 70 |
| Comparative example 2 | BPDA/PPD | PTFE/327℃ | FEP/260℃ | 250 | 0.38 | 0.40 | 72 | 75 |
As indicated in table 1, the kinetic friction coefficient of tubular articles of the present invention is low, and the contact angle of film like shaping thing is also low.In addition, from utilizing the observations of electron micrograph, confirm to have separated out fluororesin in polyimide tubulose object surfaces.And, bring installation, carry out image fixing as the photographic fixing of laser printer, consequently obtained preferable image.
Claims (15)
1. tubular articles, it is the potpourri shaping that will contain polyimide and fluororesin particle, the tubular articles that is heating and curing and forms, it is characterized in that, near at least a portion fluororesin particle in top layer that is present in described tubular articles, separate out in the outside surface of described tubular articles or surfaces externally and internally melt-flow, part or whole ground form the fluororesin tunicle.
2. tubular articles as claimed in claim 1, wherein, described fluororesin tunicle mask has the granular pattern that is caused by the fluororesin particle.
3. tubular articles as claimed in claim 1, wherein, described tubular articles is the individual layer that contains polyimide and fluororesin particle.
4. tubular articles as claimed in claim 1, wherein, described tubular articles is made of internal layer and skin; Described internal layer does not contain the fluororesin particle or compares the amount of fluororesin with skin few; Described skin is compared with internal layer, and the amount of fluororesin is big.
5. tubular articles as claimed in claim 1, wherein, the amount of fluororesin particle in the described layer that contains polyimide and fluororesin particle is 10～90 quality %.
6. tubular articles as claimed in claim 1, wherein, described fluororesin particle is at least a fluororesin that is selected from teflon, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polychlorotrifluoroethylene, tetrafluoraoethylene-hexafluoropropylene copolymer, the tetrafluoroethylene-ethylene copolymer.
7. tubular articles as claimed in claim 1, wherein, the mean grain size of described fluororesin is 0.1～100 μ m.
8. tubular articles as claimed in claim 1, wherein, described polyimide is that the polyimide precursor solution that is made of at least a kind of aromatic tetracarboxylic acid's dianhydride and at least a kind of aromatic diamine is added the polyimide that hot-imide forms.
9. the manufacture method of a tubular articles is characterized in that, the mixed solution of the fluororesin particle of polyimide precursor solution and melt-flow is coated on mold outer surface, and curtain coating is configured as the thickness of regulation; Add hot-imide, the maximum temperature of described imidizate is set at temperature above the fusing point of fluororesin; After the cooling, described mould is separated with tubular articles; Near the top layer that is present in described tubular articles at least a portion fluororesin particle is separated out in the outside surface of described tubular articles or surfaces externally and internally melt-flow, and part or whole ground form the fluororesin tunicle.
10. the manufacture method of tubular articles as claimed in claim 9, wherein, described mixed solution is being coated on before mold outer surface and curtain coating be configured as the thickness of regulation, is being configured as the thickness of regulation in advance in mold outer surface coating polyimide precursor solution and curtain coating; Before carrying out imidizate or after finishing, described mixed solution is coated on the thickness that mold outer surface and curtain coating are configured as regulation.
11. the manufacture method of tubular articles as claimed in claim 9, wherein, the amount of fluororesin particle in the described layer that contains polyimide and fluororesin particle is 10～90 quality %.
12. the manufacture method of tubular articles as claimed in claim 9, wherein, described fluororesin particle is at least a fluororesin that is selected from teflon, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polychlorotrifluoroethylene, tetrafluoraoethylene-hexafluoropropylene copolymer, the tetrafluoroethylene-ethylene copolymer.
13. the manufacture method of tubular articles as claimed in claim 9, wherein, the mean grain size of described fluororesin is 0.1～100 μ m.
14. the manufacture method of tubular articles as claimed in claim 9, wherein, described polyimide is that the polyimide precursor solution that is made of at least a kind of aromatic tetracarboxylic acid's dianhydride and at least a kind of aromatic diamine is added the polyimide that hot-imide forms.
15. the manufacture method of tubular articles as claimed in claim 14, wherein, described polyimide is that the polyimide precursor solution that is made of biphenyl tetracarboxylic dianhydride and p-phenylenediamine (PPD) is added the polyimide that hot-imide forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005044426 | 2005-02-21 | ||
| JP044426/2005 | 2005-02-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101120289A true CN101120289A (en) | 2008-02-06 |
Family
ID=36916585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800052936A Pending CN101120289A (en) | 2005-02-21 | 2006-02-20 | Tubular object and manufacturing method thereof |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20080149211A1 (en) |
| EP (1) | EP1852751A1 (en) |
| KR (1) | KR20070104898A (en) |
| CN (1) | CN101120289A (en) |
| WO (1) | WO2006088189A1 (en) |
Cited By (4)
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| CN101666998B (en) * | 2008-09-03 | 2014-09-10 | 可隆株式会社 | Seamless belt |
| CN106537259A (en) * | 2014-08-07 | 2017-03-22 | 株式会社I.S.T | Low-friction member, image-forming device, and agent for forming low-friction coating film |
| CN110292663A (en) * | 2019-06-28 | 2019-10-01 | 脉通医疗科技(嘉兴)有限公司 | A kind of preparation method and medical treatment tubing of medical treatment tubing |
| CN112574565A (en) * | 2020-12-08 | 2021-03-30 | 黄山金石木塑料科技有限公司 | Low-thermal-expansion aromatic cold-pressed polyimide resin and synthesis method and application thereof |
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|---|---|---|---|---|
| JPWO2008136467A1 (en) * | 2007-04-27 | 2010-07-29 | 株式会社アイ．エス．テイ | Coating for coating, laminate and method for producing cylindrical laminate |
| JP4685172B2 (en) * | 2009-01-20 | 2011-05-18 | シャープ株式会社 | Fixing apparatus and image forming apparatus having the same |
| DE102010062097A1 (en) * | 2010-11-29 | 2012-05-31 | Siemens Aktiengesellschaft | Flameproof fluid encapsulation |
| JP6141377B2 (en) * | 2015-10-07 | 2017-06-07 | 株式会社森清化工 | Perfluoro rubber molding |
| JP6681212B2 (en) * | 2015-11-30 | 2020-04-15 | 株式会社潤工社 | Poly-Urethane-Tube |
| US9937662B2 (en) | 2016-09-01 | 2018-04-10 | International Business Machines Corporation | Shape memory thermal interface materials |
| US9873774B1 (en) * | 2016-09-01 | 2018-01-23 | International Business Machines Corporation | Shape memory thermal interface materials |
| JP2018120121A (en) * | 2017-01-26 | 2018-08-02 | 株式会社東芝 | Fixing device |
| JP7131117B2 (en) * | 2018-06-21 | 2022-09-06 | 京セラドキュメントソリューションズ株式会社 | Fixing belt, fixing device, and image forming apparatus |
| WO2021024624A1 (en) * | 2019-08-08 | 2021-02-11 | 三菱瓦斯化学株式会社 | Flame-retardant polyimide shaping material and shaped body |
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| US4238538A (en) * | 1978-12-21 | 1980-12-09 | E. I. Du Pont De Nemours And Company | Method of and apparatus for ram-extrusion of aromatic polyimide and polyamide resins, and shaped articles formed using such method and apparatus |
| JPS6225030A (en) * | 1985-07-25 | 1987-02-03 | Ube Ind Ltd | Continuously molding method for polyimide powder |
| US5083168A (en) * | 1988-11-15 | 1992-01-21 | Canon Kabushiki Kaisha | Fixing device and fixing heater for use in the same |
| EP0436033B1 (en) * | 1989-07-21 | 1996-10-09 | Nitto Denko Corporation | Composite tubular article and its production method |
| US5471288A (en) * | 1993-03-05 | 1995-11-28 | Canon Kabushiki Kaisha | Image heating apparatus and heating film |
| JP2516310B2 (en) * | 1993-04-16 | 1996-07-24 | 日東電工株式会社 | Tubular |
| JP3054010B2 (en) * | 1993-11-15 | 2000-06-19 | 株式会社アイ．エス．テイ | Polyimide composite tubular article and method and apparatus for producing the same |
| JPH11133776A (en) * | 1997-10-30 | 1999-05-21 | Fuji Xerox Co Ltd | Fixing device and image forming device |
| JP2000298411A (en) * | 1999-04-15 | 2000-10-24 | Canon Inc | Hard fixing roller, method of manufacturing the same, and fixing device using the same |
| US6927006B2 (en) * | 2001-09-07 | 2005-08-09 | Xerox Corporation | Fuser member having fluorocarbon outer layer |
| JP2004355004A (en) * | 2003-05-28 | 2004-12-16 | Xerox Corp | Fuser member |
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2006
- 2006-02-20 KR KR1020077017720A patent/KR20070104898A/en not_active Withdrawn
- 2006-02-20 US US11/883,595 patent/US20080149211A1/en not_active Abandoned
- 2006-02-20 WO PCT/JP2006/302978 patent/WO2006088189A1/en active Application Filing
- 2006-02-20 CN CNA2006800052936A patent/CN101120289A/en active Pending
- 2006-02-20 EP EP06714118A patent/EP1852751A1/en not_active Withdrawn
Cited By (8)
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|---|---|---|---|---|
| CN101666998B (en) * | 2008-09-03 | 2014-09-10 | 可隆株式会社 | Seamless belt |
| CN106537259A (en) * | 2014-08-07 | 2017-03-22 | 株式会社I.S.T | Low-friction member, image-forming device, and agent for forming low-friction coating film |
| CN106537259B (en) * | 2014-08-07 | 2019-11-05 | 株式会社I.S.T | Low friction component, image forming apparatus and low friction overlay film forming agent |
| US10906277B2 (en) | 2014-08-07 | 2021-02-02 | I.S.T. Corporation | Low-friction member, image-forming device, and agent for forming low-friction coating film |
| CN110292663A (en) * | 2019-06-28 | 2019-10-01 | 脉通医疗科技(嘉兴)有限公司 | A kind of preparation method and medical treatment tubing of medical treatment tubing |
| WO2020258945A1 (en) * | 2019-06-28 | 2020-12-30 | 脉通医疗科技(嘉兴)有限公司 | Medical tube preparation method and medical tube |
| CN112574565A (en) * | 2020-12-08 | 2021-03-30 | 黄山金石木塑料科技有限公司 | Low-thermal-expansion aromatic cold-pressed polyimide resin and synthesis method and application thereof |
| CN112574565B (en) * | 2020-12-08 | 2023-04-25 | 黄山金石木塑料科技有限公司 | Low thermal expansion aromatic cold-pressed polyimide resin and its synthesis method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20070104898A (en) | 2007-10-29 |
| EP1852751A1 (en) | 2007-11-07 |
| US20080149211A1 (en) | 2008-06-26 |
| WO2006088189A1 (en) | 2006-08-24 |
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Open date: 20080206 |